Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor

ABSTRACT

A process for hydrocyanation of an aliphatic monoethylenically unsaturated compound, in which the ethylenic double bond is not conjugated to any other unsaturated group in the molecule, or a monoethylenically unsaturated compound in which the ethylenic double bond is conjugated to an ester group, which process uses a catalyst composition comprising a zero-valent and a multidentate phosphite ligand in the presence of a Lewis acid promoter.

FIELD OF THE INVENTION

The invention relates to a process and catalyst composition for thehydrocyanation of monoethylenically unsaturated compounds whereinzero-valent nickel and a multidentate phosphite ligand are used in thepresence of a Lewis acid promoter.

BACKGROUND OF THE INVENTION

Hydrocyanation catalyst systems, particularly pertaining to thehydrocyanation of ethylenically unsaturated compounds, are known in theart. For example, systems useful for the hydrocyanation of butadiene toform penetenenitrile (PN) and in the subsequent hydrocyanation ofpenetenenitrile to form adiponitrile (ADN), are known in thecommercially important nylon synthesis field.

The hydrocyanation of ethylenically unsaturated compounds usingtransition metal complexes with monodentate phosphite ligands isdocumented in the prior art. See, for example, U.S. Pat. Nos. 3,496,215;3,631,191; 3,655,723; and 3,766,237, and Tolman et al., Advances inCatalysis, 33, 1, 1985. The hydrocyanation of activated ethylenicallyunsaturated compounds, such as with conjugated ethylenically unsaturatedcompounds (e.g., butadiene and styrene), and strained ethylenicallyunsaturated compounds (e.g., norbornene) proceeds without the use of aLewis acid promoter, while hydrocyanation of unactivated ethylenicallyunsaturated compounds, such as 1-octene and 3-pentenenitrile, requiresthe use of a Lewis acid promoter.

Teachings regarding the use of a promoter in the hydrocyanation reactionappear, for example, in U.S. Pat. No. 3,496,217. This patent disclosesan improvement in hydrocyanation using a promoter selected from a largenumber of metal cation compounds with a variety of anions as catalystpromoters. U.S. Pat. No. 3,496,218 discloses a nickel hydrocyanationcatalyst promoted with various boron-containing compounds, includingtriphenylboron and alkali metal borohydrides. U.S. Pat. No. 4,774,353discloses a process for the preparation of dinitriles, including ADN,from unsaturated nitriles, including PN, in the presence of azero-valent nickel catalyst and a triorganotin catalyst promoter.Moreover, U.S. Pat. No. 4,874,884 discloses for producing ADN by thezero-valent nickel-catalyzed hydrocyanation of pentenenitriles in thepresence of a synergistic combination of promoters selected inaccordance with the reaction kinetics of the ADN synthesis.

Phosphite ligands have been shown to be useful ligands in thehydrocyanation of activated ethylenically unsaturated compounds. See,for example, Baker, M. J., and Pringle, P. G., J. Chem. Soc., Chem.Commun., 1292, 1991; Baker et al., J. Chem. Soc., Chem. Commun., 803,1991; Union Carbide, WO 93,03839. Also, phosphite ligands have beendisclosed with rhodium in the hydroformylation of functionalizedethylenically unsaturated compounds: see, Cuny et al., J. Am. Chem.Soc., 1993, 115, 2066.

The present invention provides a novel process and catalyst precusorcomplex which is more rapid, selective, efficient and stable thancurrent processes and catalyst complexes employed in the hydrocyanationof monoethylenically unsaturated compounds. Other objects and advantagesof the present invention will become apparent to those skilled in theart upon reference to the detailed description of the invention whichhereinafter follows.

SUMMARY OF THE INVENTION

The present invention provides a hydrocyanation process, comprisingreacting an acyclic, aliphatic, monoethylenically unsaturated compoundin which the ethylenic double bond is not conjugated to any otherolefinic group in the molecule, or a monoethylenically unsaturatedcompound in which the ethylenic double bond is conjugated to an organicester group, with a source of HCN in the presence of a catalystprecursor composition comprising a Lewis acid, a zero-valent nickel, andat least one multidentate phosphite ligand selected from the grouprepresented by the following Formulas I, II, III, IV, V, VI, and VII, inwhich all like reference characters have the same meaning, except asfurther explicitly limited. ##STR1## wherein each R¹ is independently,H, halogen, a C₁ to C₆ alkyl, or OR³ wherein R³ is a C₁ to C₆ alkyl;

each R² is independently a secondary or tertiary hydrocarbyl of 3 to 6carbon atoms;

each R^(2') is independently H, halogen, OR³ wherein R³ is a C₁ to C₆alkyl or a primary, secondary or tertiary hydrocarbyl of 1 to 6 carbonatoms; for Formula II, III, VI, VI and VII, R^(2') is at either the metaor para position to the oxygen;

each R^(5') is independently H or a primary or secondary hydrocarbyl of1 or 3 carbon atoms in either the ortho or meta position to the oxygenor CO₂ R^(3') wherein R^(3') is a C₁ to C₄ alkyl; and

each X is independently O or CH(R^(4')), wherein R^(4') is H, asubstituted phenyl, or a C₁ to C₆ alkyl;

with the proviso that the terms "secondary" and "tertiary" herein referto the carbon atom bonded to an aromatic ring;

and with the further proviso that in Formulas I, II, and V at least oneR² cannot be a tertiary hydrocarbyl.

In the above catalyst compositions, the Lewis acid is considered to be apromoter.

The present invention further provides a catalyst composition consistingessentially of zero-valent nickel and at least one multidentatephosphate ligand selected from one of Formula I, II, III, IV, V, VI andVII, as defined above.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Representative ethylenically unsaturated compounds which are useful inthe process of this invention are shown in Formula VIII or X, and thecorresponding terminal nitrile compounds produced are illustrated byFormulas IX or XI, respectively, wherein like reference characters havesame meaning. ##STR2## wherein

R⁴ is H, CN, CO₂ R⁵, or perfluoroalkyl;

y is an integer of 0 to 12;

x is an integer of 0 to 12 when R⁴ is H, CO₂ R⁵ or perfluoroalkyl;

x is an integer of 1 to 12 when R⁴ is CN; and

R⁵ is alkyl.

One of the ligands useful in the catalyst compositions of the presentinvention is illustrated above by Formula I, as defined. Alkyl groups inFormula I can be either straight chain or branched. When R¹ is OR³, R³can be primary, secondary or tertiary; examples include methyl, ethyl,isopropyl and t-butyl. In the preferred ligand, both R¹ groups are H,methoxy groups, or chlorine. As stated in the definitions of thereference characters, all of the R² groups in Formula I cannot betertiary hydrocarbyls; see Comparative Example 3 for Ligand "A2". Theterm "hydrocarbyl" is well known to the art and designates a hydrocarbonmolecule from which one hydrogen atom has been removed. Such structurecan contain single, double, or triple bonds. In the preferred Formula Iligand, R² in each occurrence is isopropyl, R¹ is methoxy, and R^(5') ishydrogen. In Formula II, X preferably is CH(Et), where Et stands forethyl, R² in each occurrence is isopropyl, R^(2') is hydrogen, and eachone of R¹ and R^(5') is methyl, where each R^(5') is in a position orthoto the oxygen atom. Again, all of the R² groups cannot be tertiaryhydrocarbyls; see Comparative Example 13 for Ligand "J2". In thepreferred Formula III ligand, each R² is isopropyl, each R^(2') ishydrogen, X is CHR^(4'), where R^(4') is 4-methoxyphenyl, and eachR^(5') is hydrogen. In the preferred Formula IV ligand, each R² group isisopropyl, and each R^(2') and R^(5') is hydrogen. In the preferredFormula V ligand, each R² group is isopropyl, each R^(2') group is parato R² methyl with the other R^(2') being hydrogens and each R^(5') ishydrogen. In the preferred Formula VI ligand, each R² group isisopropyl, each R^(2') is hydrogen, and each R^(5') is hydrogen. In thepreferred Formula VII ligand, each R² group is isopropyl, and eachR^(2') group is hydrogen and each R^(5') group is hydrogen.

The catalyst composition of the invention may be considered a"precursor" composition in that the zero-valent nickel at some pointbecomes complexed to the multidentate, phosphite ligand, and, further inall likelihood, additional reactions occur during hydrocyanation, suchas, for example, complexing of the initial catalyst composition to anethylenically unsaturated compound.

These ligands can be prepared by a variety of methods known in the art,for example, see descriptions in European Patent Application 92109599.8of Mitsubishi Kasei Corporation and the corresponding U.S. Pat. No.5,235,113 to Sato et al. The reaction of 2-isopropylphenol withphosphorus trichloride gives the phosphorochloridite. The reaction ofthis phosphorochloridite with2,2'-dihydroxy-5,5'-dimethyoxy-1,1'-biphenyl in the presence oftriethylamine gives the above-identified preferred ligand of Formula I.

The zero-valent nickel compounds can be prepared or generated accordingto techniques well known in the art, as described, for example U.S. Pat.Nos. 3,496,217;3,631,191; 3,846,461; 3,847,959; and 3,903,120, which areincorporated herein by reference. Zero-valent nickel compounds thatcontain ligands which can be displaced by the organophosphorus ligandare a preferred source of zero-valent nickel. Two such preferredzero-valent nickel compounds are Ni(COD)₂ (COD is 1,5-cyclooctadiene)and Ni(P(O-o-C₆ H₄ CH₃)₃)₂ (C₂ H₄), both of which are known in the art.Alternatively, divalent nickel compounds may be combined with a reducingagent, to serve as a source of zero-valent nickel in the reaction.Suitable divalent nickel compounds include compounds of the formula NiY₂where Y is halide, carboxylate, or acetylacetonate. Suitable reducingagents include metal borohydrides, metal aluminum hydrides, metalalkyls, Z, Fe, Al, Na, or H₂. Elemental nickel, preferably nickelpowder, when combined with a halogenated catalyst, as described in U.S.Pat. No. 3,903,120, is also a suitable source of zero-valent nickel.

The nonconjugated acyclic, aliphatic, monoethylenically unsaturatedstarting materials useful in this invention include unsaturated organiccompounds containing from 2 to approximately 30 carbon atoms.3-pentenenitrile and 4-pentenenitrile are especially preferred. As apractical matter, when the nonconjugated acyclic aliphaticmonoethylenically unsaturated compounds are used in accordance with thisinvention, up to about 10% by weight of the monoethylenicallyunsaturated compound may be present in the form of a conjugated isomer,which itself may undergo hydrocyanation. For example, when3-pentenenitrile is used, as much as 10% by weight thereof may be2-penetenenitrile. (As used herein, the term "pentenenitrile" isintended to be identical with "cyanobutene"). Suitable unsaturatedcompounds include unsubstituted hydrocarbons as well as hydrocarbonssubstituted with groups which do not attack the catalyst, such as cyano.These unsaturated compounds include monoethylenically unsaturatedcompounds containing from 2 to 30 carbons such as ethylene, propylene,butene-1, pentene-2, hexene-2, etc., nonconjugated diethylenicallyunsaturated compounds such as allene, substituted compounds such as3-pentenenitrile, 4-pentenenitrile, methyl pent-3-enoate, andethylenically unsaturated compounds having perfluoroalkyl substituentssuch as, for example, C_(Z) F_(2z+1), where z is an integer of up to 20.The monoethylenically unsaturated compounds may also be conjugated to anester group such as methyl pent-2-enoate.

The starting ethylenically unsaturated compounds useful in thisinvention and the hydrocyanation products thereof are those shown abovein Formulas VII through XI. Those of Formula VIII yield terminalnitriles of Formula IX, while those of Formula X yield terminal nitrilesof Formula XI.

Preferred are nonconjugated linear alkenes, nonconjugated linearalkenenitriles, nonconjugated linear alkenoates, linear alk-2-enoatesand perfluoroalkyl ethylenes. Most preferred substrates include 3- and4-pentenenitrile, alkyl 2-, 3-, and 4-pentenoates, and C_(Z) F_(2z+1)CH═CH₂ (where z is 1 to 12).

The preferred products are terminal alkanenitriles, lineardicyanoalkylenes, linear aliphatic cyanoesters, and3-(perfluoroalkyl)propionitrile. Most preferred products areadiponitrile, alkyl 5-cyanovalerate, C_(Z) F_(2z+1) CH₂ CH₂ CN, where zis 1 to 12.

The present hydrocyanation process may be carried out, for example, bycharging a reactor with the reactants, catalyst composition, andsolvent, if any; but preferably, the hydrogen cyanide is added slowly tothe mixture of the other components of the reaction. Hydrogen cyanidemay be delivered as a liquid or as a vapor to the reaction. Anothersuitable technique is to charge the reactor with the catalyst and thesolvent to be used, and feed both the unsaturated compound and the HCNslowly to the reaction mixture. The molar ratio of unsaturated compoundto catalyst can be varied from about 10:1 to about 2000:1.

Preferably, the reaction medium is agitated, for example, by stirring orshaking. The reaction product can be recovered by conventionaltechniques such as, for example, by distillation. The reaction may berun either batchwise or in a continuous manner.

The hydrocyanation reaction can be carried out with or without asolvent. The solvent, if used, should be liquid at the reactiontemperature and pressure and inert towards the unsaturated compound andthe catalyst. Suitable solvents include hydrocarbons, such as benzene orxylene, and nitriles, such as acetonitrile or benzonitrile. In somecases, the unsaturated compound to be hydrocyanated may itself serve asthe solvent.

The exact temperature is dependent to a certain extent on the particularcatalyst being used, the particular unsaturated compound being used andthe desired rate. Normally, temperatures of from -25° C. to 200° C. canbe used, the range of 0° C. to 150° C. being preferred.

Atmospheric pressure is satisfactory for carrying out the presentinvention and hence pressures of from about 0.05 to 10 atmospheres (50.6to 1013 kPa) are preferred. Higher pressures, up to 10,000 kPa or more,can be used, if desired, but any benefit that may be obtained therebywould probably not justify the increased cost of such operations.

HCN can be introduced to the reaction as a vapor or liquid. As analternative, a cyanohydrin can be used as the source of HCN. See, forexample, U.S. Pat. No. 3,655,723.

The process of this invention is carried out in the presence of one ormore Lewis acid promoters which affect both the activity and theselectivity of the catalyst system. The promoter may be an inorganic ororganometallic compound in which the cation is selected from scandium,titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc,boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium,rhenium and tin. Examples include ZnBr₂, ZnI₂, ZnCl₂, ZnSO₄, CuCl₂,CuCl, Cu(O₃ SCF₃)₂, CoCl₂, CoI₂, FeI₂, FeCl₃, FeCl₂ (THF)₂, TiCl₄(THF)₂, TiCl₄, TiCl₃, ClTi(OiPr)₃, MnCl₂, ScCl₃, AlCl₃, (C₈ H₁₇)AlCl₂,(C₈ H₁₇)₂ AlCl, (iso-C₄ H₉)₂)AlCl, Ph₂ AlCl, PhAlCl₂, ReCl₅, ZrCl₄,NbCl₅, VCl₃, CrCl₂, MoCl₅, YCl₃, CdCl₂, LaCl₃, Er(O₃ SCF₃)₃, Yb(O₂CCF₃)₃, SmCl₃, B(C₆ H₅)₃, TaCl₅. Suitable promoters are furtherdescribed in U.S. Pat. Nos. 3,496,217; 3,496,218; and 4,774,353. Theseinclude metal salts (such as ZnCl₂, CoI₂, and SnCl₂), and organometalliccompounds (such as RAlCl₂, R₃ SnO₃ SCF₃, and R₃ B, where R is an alkylor aryl group). U.S. Pat. No. 4,874,884 describes how synergisticcombinations of promoters can be chosen to increase the catalyticactivity of the catalyst system. Preferred promoters include CdCl₂,ZnCl₂, B(C₆ H₅)₃, and (C₆ H₅)₃ SnX, where X=CF₃ SO₃, CH₃ C₆ H₅ SO₃, or(C₆ H₅)₃ BCN. The mole ratio of promoter to nickel present in thereaction can be within the range of about 1:16 to about 50:1.

EXAMPLES

The following non-limiting, representative examples illustrate theprocess and catalyst compositions of this invention. All parts,proportions, and percentages are by weight, unless otherwise indicated.In each example, the following procedure was used unless otherwisenoted.

The mixtures were heated in a thermostatically controlled oil bath. HCNwas delivered to the flask as an HCN/N₂ gas mixture by bubbling drynitrogen carrier gas through liquid HCN maintained in an ice bath at 0°C. This provided a vapor stream which was about 35% HCN (vol/vol).Samples were periodically analyzed by gas chromatography (GC). In theexamples, ADN stands for adiponitrile, MGN stands for2-methylglutaronitrile, and ESN stands for ethylsuccinonitrile. CODstands for bis(1,5-cyclooctadiene) and THF stands for tetrahydrofuran.

Example 1 Synthesis of the ligand of Formula I where each R² isisopropyl and each R¹ is H (Ligand "A") ##STR3##

To a solution of 2.0 g of phosphochloridite derived from PCl₃ and2-isopropylphenol in 20 ml of toluene was added 0.55 g (2.95 mmoles) of2,2'-biphenol and 1.1 g (10.9 mmoles) of NEt₃ in 20 ml of toluene. Afterstirring overnight under nitrogen, the mixture was filtered throughCelite® (a product of Johns-Manville Company), and washed with toluene.The remaining solvent was removed in a rotary evaporator. Thus wasobtained 2.163 g of product as an opaque liquid. ³¹ P {1H} (121.4 MHz,C₆ D₆): 130.96 ppm. ¹ H (300 MHz, C₆ D₆): 7.51 (d, J=8Hz, 2H), 7.39 (dd,J=1.6, 7.5 Hz, 2H), 7.2-6.9 (m, 20H), 3.43 (septet, J=6.9 Hz, 4H), 1.19(d, J=6.9 Hz, 24H) along with a small amount of toluene. HRMS (HighResolution Mass Spectroscopy) calculated for C₄₈ H₅₂ O₆ P₂ : 786.3239;Found: 786.3208.

Example 1A Hydrocyanation of 3-Pentenenitrile with Ligand "A"/Ni(COD)₂ ;ZnCl₂ promoter

342 mg of Ligand "A" and 40 mg Ni(COD)₂ were dissolved in 5 ml THF. Thesolvent was removed by vacuum evaporation and 5 ml of 3PN(3-pentenenitrile) and 20 mg of ZnCl₂ were added. The mixture wastreated with HCN at a nitrogen carrier gas flow rate of 12 ml/min at 50°C. for 15 minutes. After this time, the temperature controller was setat 60° C. At 15 minute intervals, the temperature was increased to 70°,80°, and 100° C. Fifteen minutes after a temperature of 100° C. was set,GC analysis indicated 46.7% ADN, 8.0% MGN, and 1.0% ESN.

Example 1B Hydrocyanation of 3-Pentenenitrile with Ligand "A"/Ni(COD)₂ ;ZnCl₂ promoter

Ligand "A", 332 mg, and 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF.The solvent was removed by vacuum evaporation; then, 5 ml of 3PN and 20mg of ZnCl₂ were added. The mixture was treated with HCN with a nitrogencarrier gas flow rate of 12 ml/min at 70° C. for 2 hrs. GC analysisindicated 70.0% ADN, 11.6% MGN and 1.4% ESN (selectivity to ADN: 84%).

Example 1C Hydrocyanation of 3-Pentenenitrile with Ligand "A"/Ni(COD)₂ ;ZnCl₂ promoter

Ligand "A", 330 mg, and 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF.The solvent was removed by vacuum evaporation, and 5 ml of 3PN and 20 mgof ZnCl₂ were added. The mixture was treated with HCN with a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. After thistime, GC analysis indicated 26.4% ADN, 4.5% MGN and 0.6% ESN(selectivity to ADN: 84).

Example 2 Synthesis of the ligand of Formula I where each R² isisopropyl, each R^(5') is H, and each R¹ is OCH₃ (Ligand "B") ##STR4##

2,2'-Dihydroxyl-5,5'-dimethoxy-1,1'-biphenyl was prepared by thedealkylation of2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl using aprocedure described in the literature (Tashiro et al., OrganicPreparations and Procedures Int., 8, 263, 1976). Ten grams of AlCl₃ and10 g of 2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl weremixed in 125 ml of benzene and heated at 40° C. for 3 hours. The mixturewas cooled in ice, and 125 ml of 10% aqueous HCl was added slowly. Theorganic layer was separated and washed with three 125-ml portions of 10%NaOH. The basic solution was neutralized with concentrated HCl andextracted three times with 100 ml portions of ether. The ether layer wasdried over Na₂ SO₄. After filtering and removing the solvent by vacuumevaporation, the brown oil was washed with hexane; the productcrystallized from CH₂ Cl₂ /hexane, yielding 2.202 g of2,2'-dihydroxy-5,5'-dimethyoxy-1,1'-biphenyl, which was obtained as awhite solid. ¹ H (300 MHz, CD₂ Cl₂): 6.9-6.8 (m, 6H), 5.71 (s, 2H), 3.78(s, 6H).

To 2 g of phosphochloridite derived from PCl₃ and 2-isopropylphenol in20 ml of toluene was added 660 mg of the2,2'-dihydroxy-5,5'-dimethyoxy-1,1'-biphenyl prepared above and 1.01 gof NEt₃ in 20 ml of toluene. The mixture was stirred overnight andfiltered through Celite®, and washed with toluene. The solvent wasremoved to give 2.588 g of the desired product as an orange oil. ³¹ P{1H} (121.4 MHz, C₆ D₆): 131.41. ¹ H NMR (Nuclear Magnetic Resonance)(C₆ D₆): 7.4-6.4 (22H), 3.3 (m, 4H), 3.1 (s, 6H), 1.0 (m, 24H) alongwith a small amount of toluene. FBMS (Fast Atom Bombardment MassSpectroscopy): calculated M-OCH₃ : 815.36; Found: 815.07.

Example 2A Hydrocyanations of 3-Pentenenitrile with Ligand"B"/Ni(o-TTP)₂ (C₂ H₄), where o-TTP is P(O-o-C₆ H₄ CH₃)₃ ; ZnCl₂promoter

Ligand "B", 346 mg, 0.111 g of Ni(o-TTP)₂ (C₂ H₄), and 20 mg of ZnCl₂were dissolved in 5 ml of 3PN. The mixture was treated with HCN at anitrogen carrier gas flow rate of 30 ml/min at 70° C. for one hour. GCanalysis indicated 61.2% ADN, 9.9% MGN and 1.3% ESN (selectively to ADN:84.5%).

Comparative Examples 3-4A Biphenol Backbone Comparative Example 3Synthesis of the Ligand of Formula I where all R₂ are t-butyl, a t-butylgroup is meta to each R², and R¹ and R⁵ are H (Ligand "A2") ##STR5##

To 3.8 g of the chlorodite derived from PCl₃ and 2,4-di-t-butylphenol in20 ml of toluene there was added 0.75 g of 2,2'-biphenol and 0.809 g ofNEt₃ in 20 ml of toluene. The mixture was stirred overnight and thenfiltered through Celite® and washed with toluene. The solvent wasremoved in a rotary evaporator. The residue was washed withacetonitrile, and filtered to give 1.381 g of the product as a whitesolid. ³¹ P {1H} (121.4 MHz, C₆ D₆): 132.46 ppm. Also, small peaks at161.57 and 139.88 due to impurities.

Comparative Example 3A Hydrocyanation using Ligand "A2" and Ni(o-TTP)₂(C₂ H₄)

Ligand "A2", 448 mg, and 0.111 g of Ni(o-TTP)₂ (C₂ H₄) and 20 mg ofZnCl₂ were dissolved in 5 ml of 3PN. The mixture was treated with HCN ata nitrogen carrier gas flow rate of 30 ml/min at 70° C. for one hour. GCanalysis indicated 0.0% ADN, 0.05% MGN and 0.1% ESN.

Comparative Example 3B Hydrocyanation using Ligand "A2" and Ni(COD)₂

Ligand "A2", 452 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 0.0% ADN, 0.0% MGN, and 0.1% ESN.

Comparative Example 4 Synthesis of the Ligand of Formula I where R² is--CH₃ and R¹ and R^(5') and H (Ligand "A3") ##STR6##

The phosphachloridite was prepared in the usual manner by the reactionof PCl₃ with o-cresol at 0° C. in toluene, followed by fractionaldistillation at reduced pressure. It (1.85 g; 6.6 mmol) was dissolved intoluene (30 ml), and the solution was cooled to 0° C. Triethylamine (3ml) was added, followed by 2,2'-biphenol (0.56 g, 3.0 mmols). Themixture was stirred overnight at room temperature. The solids werefiltered, and the solvent was removed at a reduced pressure to give 2.26g of an lightly orange-colored liquid. ³¹ P NMR (CDCl₃): δ133.1. Also,smaller peaks at 144.5, 131.2, and 3.2 due to impurities. ¹ H NMR alsoindicated a small amount of Et₃ N/salts.

Comparative Example 4A Hydrocyanation using Ligand "A3"

Ligand "A3,", 346 mg, 0.111 g of Ni(o-TTP)₂ (C₂ H₄), and 20 mg of ZnCl₂were dissolved in 5 ml of 3PN. The mixture was treated with HCN at anitrogen carrier gas flow rate of 30 ml/min at 70° C. for one hour. GCanalysis indicated 0.0% ADN, 0.05% MGN and 0.0% ESN.

Example 5 Synthesis of the ligand of Formula II where each R² isisopropyl, each R¹, R^(2') and R^(5') is H, and X is --CH₂ -- (Ligand"C") ##STR7##

To 2 g of the phosphochloridite derived from PCl₃ with 2-isopropylphenolin 20 ml of toluene there was added 595 mg ofbis(2-hydroxyphenyl)methane and 1.01 g of NEt₃ in 20 ml of toluene. Themixture was stirred overnight, filtered through Celite®, and washed withtoluene. The solvent was removed, to give 2.514 g of the desired productas a pale yellow oil. ³¹ P {1H} (121.4 MHz, C₆ D₆): 131.33. ¹ H NMR (C₆D₆): 4.11 (s, 2H), 3.2 (m, 4H), 0.98 (d, 24H) along with aromaticresonances and a little toluene. HRMS: calculated C₄₉ H₅₄ O₆ P₂ ;800,3396; Found: 800.3017.

Example 5A Hydrocyanation of 3-Pentenenitrile with Ligand "C"/Ni(o-TTP)₂(C₂ H₄); ZnCl₂ promoter

Ligand "C", 337 mg, 0.111 g of Ni(o-TTP)₂ (C₂ H₄), and 20 mg of ZnCl₂were dissolved in 5 ml of 3PN. The mixture was treated with HCN at anitrogen flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 52.4% ADN, 11.3% MGN and 1.6% ESN (selectivity to ADN: 80%).

Example 6 Synthesis of the ligand of Formula II where each R² isisopropyl, each R^(2') is H, each R¹ and R^(5') is --CH₃, and X is--C(H)(CH₃)--(Ligand "D")) ##STR8##

To 2 g of the chlorodite derived from PCl₃ and 2-isopropylphenol in 20ml of toluene there was added 803 mg of2,2'-ethylidenebis(4,6-dimethylphenol), prepared according to Yamada etal., Bull. Chem. Soc. Jpn., 62, 3603 (1989), and 0.900 g of NEt₃ in 20ml of toluene. The mixture was stirred overnight, filtered throughCelite®, and washed with toluene. The solvent was removed to give 2.603g of the desired product as a very light-yellow oil ³¹ P {1H} (121.4MHz, C₆ D₆): 133.53. Also, minor peaks due to impurities at 133.19,131.25 and 130.36, 127.59 and 105.81 ppm. FBMS calculated for M+H:871.43; Found: 871.40.

Example 6A Hydrocyanation of 3-Pentenenitrile with Ligand "D"/Ni(COD)₂ ;ZnCl₂ promoter

Ligand "D", 366 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogenflow rate of 30 ml/min at 70° C. for one hour. GC analysis indicated55.6% ADN, 7.8% MGN and 1.4% ESN (selectivity to ADN: 86%).

Example 7 Synthesis of the ligand of Formula II were each R² isisopropyl, R^(2') is methyl, R¹ and R^(5') are H, and X is --CH₂ --(Ligand "E") ##STR9##

To 2 g of the chlorodite derived from PCl₃ and thymol in 20 ml oftoluene there was added 549 mg of bis(2-hydroxyphenyl)methane and 0.910g of NEt₃ in 20 ml of toluene. The mixture was stirred overnight,filtered through Celite®, and washed with toluene. The solvent wasremoved to give 2.379 g of the desired product as a light yellow oil. ³¹P {1H} (121.4 MHz, C₆ D₆): 131.69. Also, hour peaks due to impurities at132.24 and 130.9. FBMS: calculated C₅₃ H₂₆ O₆ P₂ : 856.41; Found:855.63.

Example 7A Hydrocyanation of 3-Penetenenitrile with Ligand "E"/Ni(COD)₂; ZnCl₂ promoter

Ligand "E", 360 mg, and 0.040 g of Ni(COD)₂ were dissolved in 5 ml ofTHF. The solvent was removed, and 20 mg of ZnCl₂ and 5 ml of 3PN wereadded. The mixture was treated with HCN at a nitrogen flow rate of 30ml/min at 70° C. for one hour. GC analysis indicated 5.8% ADN, 1.4% MGNand 0.2% ESN (selectivity to ADN: 78%).

Example 7B Hydrocyanation of 3-Pentenenitrile with Ligand "E"/Ni(COD)₂ ;ZnCl₂ promoter

Ligand "E", 360 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 70° C. for two hours. GC analysisindicated 27.4% ADN, 5.3% MGN, and 0.7% ESN (selectivity to ADN: 82.1%).

Example 8 Synthesis of the ligand of Formula II where each R² isisopropyl, each R¹ is Cl, R^(2') and R^(5') are H, and X is --CH₂ --(Ligand "F") ##STR10##

To 2 g of the phosphochloridite derived from PCl₃ and 2-isopropylphenolin 20 ml of toluene there was added 799 mg of2,2'-methylenebis(4-chlorophenol) and 900 mg of NEt₃ in 20 ml oftoluene. The mixture was stirred overnight, filtered through Celite®,and washed with toluene. The solvent was removed, to give 2,678 g of thedesired product as a light-yellow opaque oil. ³¹ P {1H} (121.4 MHz, C₆D₆): 131.6. ¹ H NMR (C₆ D₆): 4.16 (s, 2H), 3,51(m, 4H), 1.3 (d, 24H)along with aromatic resonances and a little toluene. FBMS: calculatedM+H: 869.27; Found: 868.96.

Example 8A Hydrocyanation of 3-Pentenenitrile with Ligand "F"/Ni(o-TTP)₂(C₂ H₄); ZnCl₂ promoter

Ligand "F", 337 mg, 0.111 g of Ni(o-TTP)₂ (C₂ H₄), and 20 mg of ZnCl₂were dissolved in 5 ml of 3PN. The solution was treated with HCN at anitrogen flow rate of 30 ml/min at 70° C. for one hour. After this time,GC analysis indicated 23.6% ADN, 5.3% MGN and 1.2% ESN (selectivity toADN: 79%).

Example 8B Hydrocyanation of 3-Pentenenitrile with Ligand "F"/Ni(COD)₂ ;ZnCl₂ promoter

Ligand "F", 365 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 70° C. for two hours. GC analysisindicated 51.4% ADN, 11.5% MGN, and 2.4% ESN (selectivity to ADN:82.6%).

Example 9 Synthesis of the ligand of Formula II where each R² isisopropyl; each R^(2') para to R² is methyl, each R¹ is Cl, each R^(5')is H, and X is --CH₂ -- (Ligand "G") ##STR11##

To 1.42 g of the chlorodite derived from PCl₃ and 2-isopropylphenol in20 ml of toluene there was added 523 mg of2,2'-methylenebis(4-chlorophenol) and 0.607 g of NEt₃ in 20 ml oftoluene. The mixture was stirred overnight, filtered through Celite®,and washed with toluene. The solvent was removed to give 2.07 g of thedesired product as a colorless oil. ³¹ P {1H} (121.4 MHz, C₆ D₆):131.87. FBMS: calculated M+H (M=C₅₃ H₆₀ O₆ P₁ Cl₂): 925.33; Found:925.25.

Example 9A Hydrocyanation of 3-Penetenenitrile with Ligand "G"/Ni(COD)₂; ZnCl₂ promoter

Ligand "G", 389 mg, and 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF.The solvent was removed, and 5 ml of 3PN and 20 mg of ZnCl₂ were added.The mixture was treated with HCN at a nitrogen carrier gas flow rate of30 ml/min at 70° C. for one hour. GC analysis indicated 6.1% ADN, 1.7%MGN and 0.25% ESN (selectivity to ADN: 76%).

Example 9B Hydrocyanation of 3-Pentenenitrile with Ligand "G"/Ni(COD)₂ ;ZnCl₂ promoter

Ligand "G", 389 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 79° C. for two hours. GC analysisindicated 21.2% ADN, 3.1% MGN, and 0.5% ESN (selectivity to ADN: 82.7%).

Example 10 Synthesis of the Ligand of Formula III, where each R² isisopropyl, each R^(2') and R^(5') is H, and X is --CH(p-methoxyphenyl)-(Ligand "H") ##STR12##

To 2 g of the chlorodite derived from PCl₃ and 2-isopropylphenol in 20ml of toluene was added 1.207 g of commercial p-anisylidene1,1'-(bis(2-naphthol) and 1.01 g of the NEt₃ in 20 ml of toluene. Themixture was stirred overnight, filtered through Celite®, and washed withtoluene. The solvent was removed, to give 2.916 g of the desired productas a light-yellow oil. ³¹ P {1H} (121.4 MHz, C₆ D₆): 130.10. Also, aminor peak due to an impurity at 132.52 ppm.

Example 10A Hydrocyanation using Ligand "H"

Ligand "H", 423 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogenflow rate of 30 ml/min at 70° C. for one hour. GC analysis indicated16.9% ADN, 2.8% MGN and 0.5% ESN (selectivity to ADN: 83%).

Example 10B Hydrocyanation using Ligand "H"

Ligand "H", 423 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 70° C. for two hours. GC analysisindicated 36.8% ADN, 6.6% MGN, and 1.0% ESN (selectivity to ADN: 82.6%).

Example 11 Synthesis of the Ligand of Formula II where each R² isisopropyl; each R^(2') para to R², R¹ and R^(5') is methyl, and X is--CH(CH₃)-- (Ligand "I") ##STR13##

To 2 g of the chlorodite derived from PCl₃ and thymol in 20 ml oftoluene there was added 0.741 g of2,2'-ethylidenebis(4,6-dimethylphenol), prepared according to Yamada etal., Bull. Chem. Soc. Jpn., 62, 3603 (1989), and 1.0 g of NEt₃ in 20 mlof toluene. The mixture was stirred overnight, filtered through Celite®,and washed with toluene. The solvent removed to give 2,427 g of thedesired product as a light yellow oil. ³¹ P {1H} (121.4 MHz, C₆ D₆):135.15. Also, minor peaks due to impurities at 137.10, 132.5, 132.0 and106.4 ppm. FBMS: calculated for M+H: 927.48; Found: medium-intensityion-cluster at 925.41.

Example 11A Hydrocyanation using Ligand "I"

Ligand "I", 389 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 31% ADN, 2.7% MGN and 0.4% ESN (selectivity to ADN: 91%).

Example 11B Hydrocyanation using Ligand "I"

Ligand "I", 389 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 70° C. for two hours. GC analysisindicated 48.3% ADN, 4.2% MGN, and 0.5% ESN (selectivity to ADN: 91.1%).

Example 12 synthesis of the Ligand of Formula II where each R² isisopropyl, each R^(2') is H, each R¹ and R^(5') is methyl, and X is--CH(CH₂ CH₃)-- (Ligand "J") ##STR14##

To 2 g of the chlorodite derived from PCl₃ and 2-isopropylphenol in 20ml of toluene there was added 0.845 g of2,2'-propylidenebis(4,6-dimethylphenol) (prepared according to Yamada etal., loc. cit.) and 1.0 g of NEt₃ in 20 ml of toluene. The mixture wasstirred overnight and filtered through Celite®, and washed with toluene.The solvent was removed, to give 2.77 g of the desired product as ayellow oil. ³¹ P {1H} (121.4 MHz, C₆ D₆): 134.68. Also, minor peaks dueto impurities at 136.22, 132.26, 128.6 and 105.29 ppm. FBMS: calculatedfor M+H: 885.44; Found: 885.39.

Example 12A Hydrocyanation using Ligand "J"

Ligand "J", 372 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 50 ml of 3PN. The mixture was treated with HCN at anitrogen carrier gas flow rate of 30 ml/min at 70° C. for one hour. GCanalysis indicated 67% ADN, 7.2% MGN and 0.9% ESN (selectivity to ADN:89%).

Comparative Examples 13--13B Diphenylmethane Backbone ComparativeExample 13 Synthesis of the ligand of Formula II where each R² andR^(2') para to R² is t-butyl, each R¹ and R^(5') is H, and X is --CH₂ --(Ligand "J2") ##STR15##

To 2 g of the chlorodite derived from PCl₃ and 2,4-di-t-butylphenol in20 ml of toluene was added 420 mg of bis(2-hydroxyphenyl)methane and 607mg of NEt₃ in 20 ml of toluene. The mixture was stirred overnight andfiltered through Celite®, and washed with toluene. The solvent removedto give 2.238 g of the desired product as a pale yellow oil. ³¹ P {1H}(121.4 MHz, C₆ D₆); 131.35. Also, minor peaks due to impurities at132.6, 132.0, 131.7, 131.6, 130.3, and 121.8. ppm.

Comparative Example 13A Hydrocyanations of 3-Pentenenitrile with Ligand"J2"/Ni(o-TTP)₂ (₂ H₄), where o-TTP is P(O-o-C₆ H₄ CH₃)₃ ; ZnCl₂promoter

Ligand "J2",454 mg, 0.111 g of Ni(o-TTP)₂ (C₂ H₄), and 20 mg of ZnCl₂were dissolved in 5 ml of 3PN. The mixture was treated with HCN at anitrogen carrier gas flow rate of 30 ml/min at 70° C. for one hour. GCanalysis indicated 2.0% ADN, 0.8% MGN and 0.2% ESN (selectivity to ADN:67%).

Comparative Example 13B Hydrocyanation with Ligand "J2"/Ni(COD)₂

Ligand "J2", 454 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. After thistime, GC analysis indicated 0.9% ADN, 0.4% MGN and 0.2% ESN.

Example 14 Synthesis of the Ligand of Formula II where each R² isisopropyl, each R^(2'), R^(5') and R¹ is H, and X is --O-- (Ligand "K")##STR16##

To 2 g of the chlorodite derived from PCl₃ and 2-isopropylphenol in 20ml of toluene was added 0.601 g of 2,2'-dihydroxyphenyl ether and 1.0 gof NEt₃ in 20 ml of toluene. The mixture was stirred overnight, filteredthrough Celite®, and washed with toluene. The solvent was removed togive 2.44 g of the desired product as a colorless oil. ⁻ P {1H} (121.4MHz, C₆ D₆); 131.6. Also, minor peaks due to an impurities at 132.12,and 131.8 ppm.

Example 14A Hydrocyanation using Ligand "K"

Ligand "K", 369 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 30% ADN, 7.1% MGN and 1.0% ESN (selectivity to ADN: 79%).

Example 14B Hydroxycanation using Ligand "K"

Ligand "K", 337 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 70° C. for two hours. GC analysisindicated 68.2% ADN, 15.4% MGN, and 3.2% ESN (selectivity to ADN,78.6%).

Example 15 Synthesis of the Ligand of Formula II where each R² isisopropyl, each R^(2') para to R² is methyl, each R^(5') and R¹ is H,and X is --O-- (Ligand "L") ##STR17##

To 2 g of the chlorodite derived from PCl₃ and thymol in 20 ml oftoluene was added 0.554 g of 2,2'-dihydroxyphenyl ether and 1.0 g ofNEt₃ in 20 ml of toluene. The mixture was stirred overnight, filteredthrough Celite®, and washed with toluene. The solvent removed, to give2.46 g of the desired product as a colorless oil. ³¹ P {1H} (121.4 MHz,C₆ D₆): 131.81. Also, minor peaks due to impurities at 132.3 and 132.0ppm.

Example 15A Hydrocyanation using Ligand "L"

Ligand "L", 359 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. After thistime, GC analysis indicated 55% ADN, 12.0% MGN and 1.0% ESN (selectivityto ADN: 80%).

Example 16 Synthesis of the ligand of Formula II where each R² isisopropyl, each R^(2') is H, each R^(5') and R¹ is methyl, and X is--CH(CH₃)-- (Ligand "D2") ##STR18##

To 2 g of the chlorodite derived from PCl₃ and 2-isopropylphenol in 20ml of toluene was added 803 mg of2,2'-ethylidenebis(4,5-dimethylphenol), prepared according to Yamada etal., op. cit., and 1 g of NEt₃ in 20 ml of toluene. The mixture wasstirred overnight, filtered through Celite®, and washed with toluene.The solvent was removed, to give 2.541 g of the desired product as anopaque oil. ³¹ P {1H} (121.4 MHz, C₆ D₆): 130.7 Minor peaks at 132.06,131.14, and 130.14.

Example 16A Hydrocyanation of 3-Pentenenitrile with Ligand "D2"/Ni(COD)₂; ZnCl₂ promoter

370 mg of Ligand "D2", 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogenflow rate of 30 ml/min at 70° C. for one hour. GC analysis indicated24.7% ADN, 6.0% MGN and 0.7% ESN (selectivity to ADN: 79%).

Example 16B Hydrocyanation of 3-Pentenenitrile with Ligand "D2"/Ni(COD)₂; ZnCl₂ promoter

Ligand "D2", 366 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF.The solvent was removed by vacuum evaporation. To the residue was added5 ml of 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 12 ml/min at 70° C. for two hours. GC analysisindicated 36.2% ADN, 8.7% MGN, and 1.0% ESN (selectivity to ADN: 79.0%).

Example 17 Synthesis of the ligand of Formula IV, where each R² isisopropyl, and each R^(2') and R^(5') is H (Ligand "M") ##STR19##

To 20 ml of a toluene solution containing 1.145 g of 2,2'-binaphthol and1.21 g of NEt₃ at -40° C. was added 1.0 g of 1,1'-biphenyl-2,2'-diylphosphorochloridite in 20 ml of toluene. The mixture was warmed to roomtemperature and stirred overnight. A 20 ml toluene solution contaningthe chloridite derived from PCl₃ and 2-isopropylphenol was addedthereto. After stirring for two days, the mixture was filtered throughCelite®, and washed with toluene. The solvent was removed, to give 3.382g of tan solid. ³¹ P {1H} (121.4 MHz, C₆ D₆): 145.3 δ, 131.2 δ. Alsominor peaks due to impurities at 146.6, 146.4, 146.3, 132.2, and 131.0.FBMS: Found: 885.20. The FBMS data is inconsistent with the structureshown for Ligand "M" due to the possible presence of an impurity.

Example 17A Hydrocyanation of 3-Penetenenitrile with Ligand"M"/Ni(o-TTP)₂ (C₂ H₄); ZnCl₂ promoter

Ligand "M", 331 mg, 0.111 g of Ni(o-TTP)₂ (C₂ H₄), and 20 mg of ZnCl₂were dissolved in 5 ml of 3PN. The mixture was treated with HCN at anitrogen flow rate of 30 ml/min at 70° C. for one hour. After this time,GC analysis indicated 19.2% ADN, 3.7% MGN and 0.7% ESN (selectivity toADN: 81%).

Example 17B Hydrocyanation of 3-Pentenenitrile with Ligand "M"/Ni(COD)₂; ZnCl₂ promoter

344 mg of Ligand "M" and 0.040 g of Ni(COD)₂ and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN with anitrogen flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 41% ADN, 7.1% MGN and 1.1% ESN (selectivity to ADN: 83%).

Example 18 Synthesis of the ligand of Formula V, where each R² isisopropyl, and each R^(2') and R^(5') is H (Ligand "N") ##STR20##

To 2 g of the phosphochloridite derived from PCl₃ and 2-isopropylphenolin 20 ml of toluene was added 850 mg of 1,1'-bi-2-naphthol and 1.2 g ofNEt₃ in 20 ml of toluene. The mixture was stirred overnight, filteredthrough Celite®, and washed with toluene. The solvent was removed, togive 2.711 g of the desired product as a yellow liquid. ³¹ P {1H} (121.4MHz, C₆ D₆): 131.51. FBMS calculated for M+1 for the desired product C₅₆H₅₆ O₆ P₂ : 887.36; Found 887.37.

Example 18A Hydrocyanation of 3-Pentenenitrile with Ligand "N"/Ni(COD)₂; ZnCl₂ promoter

Ligand "N", 373 mg, and 0.040 g of Ni(COD)₂ were dissolved in 5 ml of3PN containing 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 21.5% ADN, 3.3% MGN and 0.5% ESN (selectivity to ADN: 85%).

Example 18B Hydrocyanation of 3-Pentenenitrile with Ligand "N"/Ni(COD)₂; ZnCl₂ promoter

Ligand "N", 373 mg, 40 mg of Ni(COD)₂ were dissolved in 5 ml of THF. Thesolvent was removed by vacuum evaporation. To the residue was added 5 mlof 3PN and 20 mg of ZnCl₂. The mixture was treated with HCN at anitrogen flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 58.9% ADN, 9.2% MGN, and 1.1% ESN (selectivity to ADN: 83.3%).

Example 19 Synthesis of the ligand of Formula V, where each R² isisopropyl, each R^(2') para to R² is methyl and the other R^(2') is H,and each R^(5') is H (Ligand "O") ##STR21##

To 20 ml of toluene solution containing 2.0 g of the phosphorochloriditederived from PCl₃ and thymol were added 0.785 g of 1,1'-bi2-naphthol and0.910 g of NEt₃ in 20 ml of toluene. The mixture was stirred overnight.The mixture was filtered through Celite®, and washed with toluene. Thesolvent was removed, to give 2.569 g of an orange oil. ³¹ P {1H} (121.4MHz, C₆ D₆): 131.246. Also minor peaks due to impurities at 145.73 and132.31. FBMS:

Found: 941.64; calculate for C₆₀ H₆₄ O₆ P₂ : 942.42.

Example 19A Hydrocyanations of 3-Pentenenitrile with Ligand "O"/Ni(COD)₂; ZnCl₂ promoter

Ligand "O", 395 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogenflow rate of 30 ml/min at 70° C. for one hour. GC analysis indicated 63%ADN, 8.0% MGN and 0.8% ESN (selectivity to ADN: 88%).

Comparative Example 20 Synthesis of the ligand of Formula V, where eachR² and R^(2') para to R² is t-butyl, other R^(2') is H and each R^(5')is H (Ligand "P") ##STR22##

Phosphorus trichloride (0.55 g, 4.0 mmols) was dissolved in toluene (10ml) and cooled in an ice/salt bath. 2,6-Di-t-butyl phenol (1.65 g, 8.0mmols) and triethylamine (2.1 ml; 15 mmols) were dissolved in toluene(10 ml). This solution was added dropwise to the cold PCl₃ solution.After 30 min, the mixture was heated to reflux for 75 minutes. Themixture was again cooled in the ice bath, and a solution of1,1'-bi(2-naphthol) (0.57 g; 2.0 mmol) in toluene was added dropwise.The reaction mixture was heated to reflux for 1.5 hours. The mixture wascooled, and the solids were removed by filtration. The solvent wasremoved in vacuo, leaving a sticky yellow solid. Recrystallization fromacetonitrile was unsuccessful because the material was fairly soluble.The acetonitrile was removed to give a pale yellow solid. ³¹ P NMR(CDCl₃): δ129.7. Also, small peaks at 130.8 and 145.6 due to impurities.

Comparative Example 20A Hydrocyanation using Ligand P

Ligand "P", 490 mg, 0.040 g of Ni(COD)₂, and 20 mg of ZnCl₂ weredissolved in 5 ml of 3PN. The mixture was treated with HCN at a nitrogencarrier gas flow rate of 30 ml/min at 70° C. for one hour. GC analysisindicated 3.7% ADN, 0.7% MGN and 0.4% ESN (selectivity to ADN: 77%).

Examples 22-31 Hydrocyanation of 3-Pentenenitrile

Table 1 shows hydrocyanations using a variety of ligands of theinvention, prepared in accordance with the general procedures describedin the previous examples. The specific conditions for eachhydrocyanation are described as Method A, B or C.

Comparative Examples A-C2 Hydrocyanation of 3-Pentenenitrile usingp-tritolylphosphite Comparative Example A Compares to Method A of Table1

To 5 ml of THF was added 0.296 g (0.84 mmoles) of p-tritolylphosphiteand 0.040 g (0.14 mmoles) of Ni(COD)₂. The solvent was removed by vacuumevaporation. To the residue was added 5 ml of 3PN and 20 mg of ZnCl₂.The mixture was treated with HCN at a nitrogen flow rate of 30 ml/min at70° C. for one hour. GC analysis indicated 37.5% ADN, 8.4% MGN and 1.3%ESN (selectivity to ADN: 79.4%)

Comparative Example B Compares to Method B of Table 1

To 5 ml of 3PN was added 0.306 g (0.89 mmoles) of p-tritolylphosphiteand 0.115 g (0.14 mmoles) of (oTTP)₂ Ni(ethylene)(oTTP=o-tritolylphosphite) and 0.020 g of ZnCl₂. The mixture was treatedwith HCN at a nitrogen flow rate of 30 ml/min at 70° C. for one hour. GCanalysis indicated 28.6% AND, 5.9% MGN and 0.9% ESN (selectivity to ADN:80.7%).

Comparative Example C1 Compares to Method C of Table 1

296 mg of p-tritolylphosphite and 40 mg of Ni(COD)₂ were dissolved in 5ml of THF. The solvent was removed by vacuum evaporation. To the residuewas added 5 ml of 3PN and 20 mg of ZnCl₂. The mixture was treated withHCN at a nitrogen flow rate of 12 ml/min at 70° C. for two hours. GCanalysis indicated 22.7% ADN, 5.1% MGN, and 0.8% ESN (selectivity toADN: 79.4%).

Comparative Example C2 Compares to Method C of Table 1

To 5 ml of 3PN was added 0.099 g (0.28 mmoles) of p-tritolylphosphite,0.205 g (0.14 mmoles) of tetrakis(p-tritolylphosphite)nickel and 20 mgof ZnCl₂. The mixture was treated with HCN at a nitrogen flow rate of 12cc/min. After 1 hr of reaction, GC analysis indicated 26.5% ADN, 5.9%MGN and 0.8% ESN (selectivity to ADN: 79.8%). After 2 hr of reaction, GCanalysis indicated 27.6% ADN, 6.1% MGN, 0.9% ESN (selectivity to ADN:79.8%)

                                      TABLE 1    __________________________________________________________________________    Example                                    Hydrocyanation    No.  Ligand Structure           Conversion                                          % ADN                                               Method    __________________________________________________________________________    22          ##STR23##                 19.0  92.4 A    23          ##STR24##                 6.7   88.3 A    24          ##STR25##                 28.7  91.6 A    25          ##STR26##                 6.3   91.2 A    26          ##STR27##                 77.5  90.1 A    27          ##STR28##                 25.9  89.1 C    28          ##STR29##                 24.3  89.9 A    29          ##STR30##                 41.0  83.9 B    30          ##STR31##                 46.9  84.8 A    31          ##STR32##                 15.8  86.1 C    __________________________________________________________________________

Method A: 0.42 mmoles ligand, 0.14 mmoles Ni(COD)₂ in 5 ml THF. Removesolvent. 5 ml 3PN and 20 mg ZnCl₂. HCN at 30 ml/min for 1 hr.

Method B: 0.42 mmoles ligand, 0.14 mmoles Ni(COD)₂ in 5 ml 3PN and 20 mgZnCl₂. HCN at 30 ml/min for 1 hr.

Method C: 0.42 mmoles ligand, 0.14 mmoles Ni(COD)₂ in 5 ml THF. Removesolvent. 5 ml 3PN and 20 mg ZnCl₂. HCN at 12 ml/min for 2 hours.##STR33##

Although particular embodiments of the present invention have beendescribed in the foregoing description, it will be understood by thoseskilled in the art that the invention is capable of numerousmodifications, substitutions and rearrangements without departing fromthe spirit or essential attributes of the invention. Reference should bemade to the appended claims, rather than to the foregoing specification,as indicating the scope of the invention.

We claim:
 1. A hydrocyanation process comprising reacting an acyclic,aliphatic, monoethylenically unsaturated compound in which the ethylenicdouble bond is not conjugated to any other olefinic group in themolecule, or a monoethylenically unsaturated compound in which theethylenic double bond is conjugated to an organic ester group, with asource of HCN in the presence of a catalyst composition comprising aLewis acid, a zero-valent nickel, and at least one multidentatephosphite ligand selected from the group represented by the followingFormulas I, II, III, IV, V, VI and VII: ##STR34## wherein each R¹ isindependently, H, halogen, a C₁ to C₆ alkyl, or OR³ wherein R³ is a C₁to C₆ alkyl;each R² is independently a secondary or tertiary hydrocarbylof 3 to 6 carbon atoms; each R^(2') is independently H, halogen, OR³wherein R³ is a C₁ to C₆ alkyl or a primary, secondary or tertiaryhydrocarbyl of 1 to 6 carbon atoms; for Formulas II, III, IV, VI andVII, R^(2') is at either the meta or para position to the oxygen; eachR^(5') is independently H or a primary or secondary hydrocarbyl of 1 to3 carbon atoms in either the ortho or meta position to the oxygen or CO₂R^(3') where R^(3') is a C₁ to C₄ alkyl; and each X is independently Oor CH(R^(4')), wherein R^(4') is H, a substituted phenyl, or a C₁ to C₆alkyl;with the proviso that the terms "secondary" and "tertiary" hereinrefer to the carbon atom bonded to an aromatic ring; and with thefurther proviso that in Formulas I, II, and V at least one R² cannot bea tertiary hydrocarbyl.
 2. The process of claim 1 wherein the startingethylenically unsaturated compound is selected from the group consistingof the compounds of the following formulas VIII and X:

    CH.sub.3 --(CH.sub.2).sub.y --CH═CH--(CH.sub.2).sub.x --R.sup.4(VIII)

    CH.sub.2 ═CH--(CH.sub.2).sub.x --R.sup.4               (X)

wherein R⁴ is H, CN, CO₂ R⁵, or perfluoroalkyl; y is an integer of 0 to12; x is an integer of 0 to 12 when R⁴ is H, CO₂ R⁵ or perfluoroalkyl; xis an integer of 1 to 12 when R⁴ is CN; and R⁵ is alkyl.
 3. The processof claim 1 wherein the starting ethylenically unsaturated compound isselected from the group consisting of 3-pentenenitrile,4-pentenenitrile; alkyl 2-, 3-, and 4-pentenoates, and C_(z) F_(2z+1)CH═CH₂, where z is an integer of 1 to
 12. 4. The process of claim 3wherein the starting ethylenically unsaturated compound is3-pentenenitrile or 4-pentenenitrile.
 5. The process of claim 1 which iscarried out at a temperature of -25° C. to 200° C. and at a pressure of50.6 to 1013 kPa.
 6. The process of claim 5 which is carried out atatmospheric pressure and at a temperature of 0° C. to 150° C.
 7. Theprocess of claim 1 wherein the Lewis acid is selected from the groupconsisting of inorganic or organometallic compounds in which the cationis selected from scandium, titanium, vanadium,chromium, manganese, iron,cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium,molybdenum, cadmium, rhenium and tin.
 8. The process of claim 7 whereinthe Lewis acid is selected from the group consisting of ZnBr₂, ZnI₂,ZnCl₂, ZnSO₄, CuCl₂, CuCl, Cu(O₃ SCF₃)₂, CoCl₂, CoI₂, FeI₂, FeCl₃, FeCl₂(tetrahydrofuran)₂, TiCl₄ (tetrahydrofuran)₂, TiCl₄, TiCl₃, ClTi(OiPr)₃,MnCl₂, ScCl₃, AlCl₃, (C₈ H₁₇)AlCl₂, (C₈ H₁₇)₂ AlCl, (iso-C₄ H₉)₂ AlCl,(phenyl)₂ AlCl, phenylAlCl₂, ReCl₅, ZrCl₄, NbCl₅, VCl₃, CrCl₂, MoCl₅,YCl₃, CdCl₂, LaCl₃, Er(O₃ SCF₃)₃, Yb(O₂ CCF₃)₃, SmCl₃, TaCl₅, CdCl₂,B(C₆ H₅)₃, and (C₆ H₅)₃ SnX, where X=CF₃ SO₃, CH₃ C₆ H₅ SO₃, or (C₆ H₅)₃BCN.